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EP3031607B1 - Moulage multicouche - Google Patents

Moulage multicouche Download PDF

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Publication number
EP3031607B1
EP3031607B1 EP14833945.0A EP14833945A EP3031607B1 EP 3031607 B1 EP3031607 B1 EP 3031607B1 EP 14833945 A EP14833945 A EP 14833945A EP 3031607 B1 EP3031607 B1 EP 3031607B1
Authority
EP
European Patent Office
Prior art keywords
resin
polyester resin
multilayer
layer
surface layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14833945.0A
Other languages
German (de)
English (en)
Other versions
EP3031607A4 (fr
EP3031607A1 (fr
Inventor
Kazunobu Sato
Atsuko Iwasaki
Takanori Miyabe
Tomoe SUNADA
Hirokatsu ARAI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
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Publication date
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Publication of EP3031607A1 publication Critical patent/EP3031607A1/fr
Publication of EP3031607A4 publication Critical patent/EP3031607A4/fr
Application granted granted Critical
Publication of EP3031607B1 publication Critical patent/EP3031607B1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B29C49/0411—Means for defining the wall or layer thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08—Biaxial stretching during blow-moulding
    • B29C49/16—Biaxial stretching during blow-moulding using pressure difference for pre-stretching, e.g. pre-blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3032—Preforms or parisons made of several components having components being injected
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3041—Preforms or parisons made of several components having components being extruded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/258—Tubular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a multilayer molding, and specifically relates to a multilayer molding, in which delamination of the multilayer molding at the time of transport thereof or impact caused by drop is prevented by improving interlayer adhesion between the surface layer and the core layer, and in which delamination can be avoided without employing a shape in which the concavo-convex portion or bent portion is few, and which realizes high design flexibility.
  • plastic vessels mainly made of polyester such as polyethylene terephthalate (PET) are widely used for tea, fruit juice drink, carbonated drink, etc.
  • PET polyethylene terephthalate
  • the ratio of small plastic bottles in plastic vessels has been increasing over time.
  • the bottle is miniaturized, the ratio of the surface area per unit volume increases, and therefore, when the bottle is miniaturized, the expiration date of the content tends to be shortened.
  • reduction in the thickness and weight of vessels has been promoted, and it has been demanded to further improve barrier properties.
  • a bottle obtained by performing biaxial stretch blow molding of a parison having a three-layer or five-layer structure which is obtained by injecting a thermoplastic polyester resin such as PET forming the surface layer and a thermoplastic gas-barrier resin such as polymethaxylylene adipamide (polyamide MXD6) to fill a mold cavity, has been put to practical use.
  • a thermoplastic polyester resin such as PET forming the surface layer
  • a thermoplastic gas-barrier resin such as polymethaxylylene adipamide (polyamide MXD6)
  • a resin having oxygen trapping function which traps oxygen in a vessel while blocking oxygen from the outside of the vessel, has been developed, and it is applied to multilayer bottles.
  • a bottle having oxygen trapping properties a multilayer bottle in which polyamide MXD6 is mixed with a transition metal-based catalyst to be used as a gas barrier layer is preferable from the viewpoint of the oxygen absorption rate, transparency, strength, moldability, etc.
  • the above-described multilayer bottle is utilized as a vessel for beer, tea, carbonated drink, etc. because of its good gas barrier properties.
  • the quality of the content is maintained and the shelf life is improved.
  • the commercial value may be reduced because delamination may be caused among different types of resins, for example, among the outer surface layer, the inner surface layer and the core layer.
  • Patent Document 1 a technique of improving delamination resistance, in which a roughly-mixed resin is positioned between layers by using a back-flow control apparatus which can provide a constant amount of back-flow to the gas barrier layer side at the time of finally injecting a resin constituting the surface layer into a mold cavity, is disclosed (Patent Document 1).
  • Patent Documents 2 and 3 a method for suppressing delamination by using a mixed layer made of a polyester resin and a gas-barrier resin as a core layer is disclosed.
  • Patent Document 4 As one example of a multilayer sheet and multilayer vessel obtained by molding the multilayer sheet, a laminate in which an adhesive layer is provided between a polyester-based resin layer and a gas-barrier resin layer is known (Patent Document 4).
  • Patent Document 5 discloses a heating polyester resin structure having a resin layer containing a polyester resin having a cyclic acetal skeleton in a diol unit.
  • Patent Document 1 disclosing the improvement of delamination resistance of the multilayer bottle, there is a problem that a special apparatus is required. Further, in the method of using the mixed layer made of a polyester resin and a gas-barrier resin as the core layer, there is not only a problem of reduction in transparency, but also a problem of reduction in gas barrier properties due to addition of a large amount of the polyester resin.
  • the adhesive layer is provided between the surface layer and the gas barrier layer, and for this reason, an extruder for forming the adhesive layer is required, resulting in increase of the production cost.
  • the purpose of the present invention is to solve the above-described problems to provide a multilayer molding having excellent transparency and gas barrier properties, wherein delamination due to drop or impact does not easily occur.
  • the present inventors diligently made researches on delamination resistance of the multilayer molding, and found that a multilayer molding, in which at least one resin layer in contact with a layer made by mixing a polyamide with a specific polyester contains a predetermined amount of a polyester resin, can improve adhesiveness between layers and prevent delamination at the time of drop or impact and has excellent transparency and gas barrier properties, and thus the present invention was achieved.
  • the present invention is as follows:
  • the present invention it is possible to obtain a multilayer molding having excellent transparency and gas barrier properties, wherein delamination does not easily occur, and therefore the present invention has significance for industry.
  • the resin-made multilayer molding of the present invention is a multilayer molding including three or more resin layers, wherein the resin layers forming both the surfaces of the molding are configured from a resin containing 70 wt% or more of the polyester resin (A). It is advantageous to use a resin containing 70 wt% or more of the polyester resin (A) as the resin layers forming the surfaces in terms of transparency, mechanical strength and moldability.
  • the polyester resin (A) to be used in the multilayer molding of the present embodiment is a polyester obtained by polymerizing a dicarboxylic acid component containing 80 mol% or more, and preferably 90 mol% or more of terephthalic acid and a diol component containing 80 mol% or more, and preferably 90 mol% or more of ethylene glycol.
  • a molding having excellent aroma retaining properties can be obtained.
  • polyester resin (A) polyethylene terephthalate can be suitably used. In this case, excellent transparency, mechanical strength, injection-molding processability and stretch blow moldability, all of which are possessed by polyethylene terephthalate, can be exerted.
  • dicarboxylic acid components other than terephthalic acid isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4- or 2,6-dicarboxylic acid, adipic acid, sebacic acid, decane-1,10-carboxylic acid and hexahydroterephthalic acid can be used.
  • diol components other than ethylene glycol propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexane dimethanol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyethoxyphenyl)propane and the like can be used.
  • oxyacids such as p-oxybenzoic acid can also be used.
  • the limiting viscosity of the polyester resin (A) is 0.55 to 1.50 (dL/g), and preferably 0.65 to 1.40 (dL/g).
  • the limiting viscosity is 0.55 (dL/g) or more as described above, it is possible to obtain a multilayer parison in a transparent amorphous state, and the mechanical strength of a multilayer molding obtained is satisfactory.
  • the limiting viscosity is 1.50 (dL/g) or less as described above, it is possible to avoid troubles of molding caused by increase in the viscosity.
  • thermoplastic resins include thermoplastic polyester resins such as polyethylene-2,6-naphthalene dicarboxylate, polyolefin-based resins, polycarbonate, polyacrylonitrile, polyvinyl chloride and polystyrene. It is also possible to use end materials generated in the process of producing the multilayer molding of the present invention as other thermoplastic resins.
  • the blending amount of the other thermoplastic resins is less than 30 wt%, preferably 20 wt% or less, and more preferably 10 wt% or less of the resin constituting the resin layer including the polyester resin (A).
  • At least one layer is formed by a mixed resin (B) containing a polyamide resin (C) and a specific polyester resin (D) described below.
  • the polyamide resin (C) is obtained by polymerizing a diamine component containing 70 mol% or more of m-xylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid.
  • a diamine component containing 70 mol% or more of m-xylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid When the amount of m-xylylenediamine in the diamine component is 70 mol% or more, excellent gas barrier properties can be maintained.
  • the amount of adipic acid in the dicarboxylic acid component is 70 mol% or more, it is possible to prevent reduction in gas barrier properties and crystallizability.
  • polyamide MXD6 polymethaxylylene adipamide
  • polyester resin (A) polyethylene terephthalate
  • diamine components other than m-xylylenediamine to be used include, but are not limited to: aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(amino
  • dicarboxylic acid components other than adipic acid include, but are not limited to, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
  • polyamide resin (C) may contain a small amount of monoamine or monocarboxylic acid to be used as a molecular weight modifier at the time of the production.
  • the above-described polyamide resin (C) is produced by the melt polycondensation (melt polymerization) method or carrying out melt polycondensation and then solid phase polymerization.
  • a nylon salt consisting of a diamine component and a dicarboxylic acid component is heated under pressure in the presence of water and then polymerized in a molten state while removing the water added and condensation water.
  • the polyamide resin (C) can also be produced by a method in which a diamine component is directly added to a dicarboxylic acid component in a molten state to be subjected to polycondensation.
  • the diamine component is continuously added to the dicarboxylic acid component in order to keep the reaction system in a homogeneous liquid state while allowing the polycondensation to proceed with the reaction system being heated in order to prevent the reaction temperature from being lowered below the melting points of oligoamides and polyamides produced.
  • a phosphorus atom-containing compound may be added to the polycondensation system of the polyamide resin (C).
  • the phosphorus atom-containing compound include dimethylphosphinic acid, phenyl methyl phosphinic acid, hypophosphoric acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylphosphonous acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid, sodium
  • metal hypophosphites such as sodium hypophosphite, potassium hypophosphite and lithium hypophosphite are preferably used because of excellent effects of promoting an amidation reaction and preventing coloring thereof, and sodium hypophosphite is particularly preferred, but the phosphorus atom-containing compound which can be used in the present invention is not limited to these compounds.
  • the amount of the phosphorus atom-containing compound to be added to the polycondensation system of the polyamide resin (C) is preferably 1 to 500 ppm, more preferably 5 to 450 ppm, and even more preferably 10 to 400 ppm when converted to the phosphorus atom concentration in the polyamide resin (C).
  • an alkali metal compound in combination with the phosphorus atom-containing compound to the polycondensation system of the polyamide resin (C).
  • an alkali metal compound or alkaline earth metal compound it is preferred to allow an alkali metal compound or alkaline earth metal compound to coexist.
  • alkali metal/alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide
  • alkali metal/alkaline earth metal acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate and barium acetate.
  • the value obtained by dividing the mole number of the compound by the mole number of the phosphorus atom-containing compound is set to preferably 0.5 to 2.0, more preferably 0.6 to 1.8, and even more preferably 0.7 to 1.5.
  • the polyamide resin (C) obtained by melt polycondensation is taken out, pelletized, and then dried to be used. It may be further subjected to solid phase polymerization in order to increase the polymerization degree.
  • a heating apparatus to be used for drying or solid phase polymerization a continuous heating and drying apparatus, a rotary drum type heating apparatus such as those called tumble dryer, conical dryer, rotary dryer, etc., and a conical heating apparatus equipped with a rotary wing inside called Nauta mixer can be suitably used.
  • the heating apparatus is not limited thereto, and a publicly-known method and apparatus can be used.
  • a batch-type heating apparatus is particularly preferably used because the system can be sealed and it is easier to perform polycondensation in a state in which oxygen that causes coloring is removed.
  • the degree of coloring is low and the ratio of gel is low.
  • a polyamide having a b* value of 5 or less in the color difference test according to JIS-K-7105 is preferably used.
  • the b* value of the polyamide is more preferably 3 or less, and even more preferably 1 or less.
  • the relative viscosity of the polyamide resin (C) is preferably 1.5 to 4.2, more preferably 1.6 to 4.0, and even more preferably 1.7 to 3.8.
  • the terminal amino group concentration of the polyamide resin (C) to be used in the present embodiment is preferably 10 to 40 ⁇ -equivalent/g, more preferably 12 to 35 ⁇ -equivalent/g, and even more preferably 15 to 30 ⁇ -equivalent/g.
  • terminal amino group concentration within the above-described range, gelation caused by increase in heat history of the polyamide resin (C) is suppressed, and yellowing of outer appearance caused by a reaction between acetaldehyde generated from the polyester resin (A) and the terminal amino group is also suppressed.
  • Examples of means for setting the terminal amino group concentration within the above-described range include a method in which polymerization is progressed in a manner such that the amount of dicarboxylic acid becomes slightly excessive with respect to the molar ratio between the diamine component and the dicarboxylic acid component, and a method in which the terminal amino group is capped by adding a monocarboxylic acid compound, a dicarboxylic anhydride or the like after the reaction is completed, but the means is not limited to these methods, and various methods can be used.
  • the content of m-xylylenediamine remaining in the polyamide resin (C) is set to be preferably 10 ppm or less, more preferably 5 ppm or less, and even more preferably 1 ppm.
  • Examples of means for setting the content of m-xylylenediamine to 10 ppm or less include a method in which polyamide after polymerization is heated under reduced pressure, and a method in which melting is carried out using an extruder or the like and the pressure in the system is reduced, but the means is not limited to these methods, and various methods can be used.
  • an oligomer consisting of the dicarboxylic acid component and the diamine component may be mixed in the polyamide resin (C).
  • a monomer in which m-xylylenediamine and adipic acid are cyclized may rise to the surface of the molding at the time of the melt process, resulting in poor outer appearance of the molding.
  • the amount of the above-described cyclic monomer contained in the polyamide resin (C) is set to be preferably 1 wt% or less, more preferably 0.8 wt% or less, and even more preferably 0.5 wt% or less.
  • molded products having good outer appearance can be produced continuously for a long period of time.
  • means for reducing the content of the cyclic monomer include a method in which the polyamide resin (C) is washed with water, a method in which the treatment is carried out at a high temperature and in a high vacuum environment, and a method in which removal is carried out with the pressure in an extruder being reduced at the time of melting and extruding, but the means is not limited to these methods, and publicly-known methods for removing a low-molecular weight or volatile component can be suitably employed.
  • polyamide is crushed by means of freezing and crushing, then extraction is carried out at 80°C for 1 hour using methanol as a solvent, and analysis is carried out by means of liquid chromatography.
  • Additives such as an antioxidant, a delustering agent, a heat-resistance stabilizer, a weathering stabilizer, an ultraviolet absorber, a nucleating agent, a plasticizer, a flame retardant, an antistatic agent, a color protection agent, a lubricant and an antigelling agent, clays such as layered silicate, nanofillers, etc. can also be added to the polyamide resin (C) within a range in which the effects of the present invention are not reduced.
  • various polyamides such as Nylon 6, Nylon 66 and amorphous nylons in which an aromatic dicarboxylic acid is utilized as a monomer and modified resins thereof, polyolefins and modified resins thereof, elastomers having styrene in the skeleton thereof, etc. can be added to the polyamide resin (C) for the purpose of modification of the polyamide resin (C), but such additives are not limited to the above-described substances, and various materials may be mixed together. Furthermore, it is possible to product a multilayer molding having oxygen absorption function by allowing cobalt metal to exist in the multilayer molding of the present invention to induce an oxidation reaction of the polyamide resin (C).
  • the polyester resin (A) and/or the polyester resin (D), wherein a cobalt compound is used as one of polymerization catalysts may be utilized.
  • a cobalt compound may be melted and mixed with the polyester resin (A) and/or the polyester resin (D) and/or the polyamide resin (C) in advance for utilization.
  • a cobalt compound may be mixed with the polyester resin (A) and/or the polyester resin (D) and/or the polyamide resin (C) at the time of producing the multilayer molding.
  • cobalt carboxylates such as cobalt octanoate, cobalt naphthenate, cobalt acetate and cobalt stearate are preferably used.
  • the concentration of cobalt metal relative to the weight of the multilayer molding is preferably 10 to 1000 ppm, more preferably 30 to 600 ppm, and even more preferably 50 to 400 ppm. By setting the concentration within the above-described range, effective oxygen absorption function can be imparted to the multilayer molding.
  • the above-described cobalt compound functions as a catalyst for an oxidation reaction of an organic compound having an unsaturated carbon bond as well as the polyamide resin (C).
  • polymers of unsaturated hydrocarbons such as polybutadiene and polyisoprene and oligomers thereof, and compounds to which a functional group is added for improving compatibility can also be added.
  • the polyester resin (D) to be used in the present embodiment is a polyester, which contains a dicarboxylic acid unit and a diol unit, and which contains a diol unit having a cyclic acetal skeleton as the diol unit.
  • the diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by general formula (1) or (2) below:
  • R 1 and R 2 each independently represent a divalent hydrocarbon group selected from the group consisting of a C 1-10 divalent aliphatic hydrocarbon group, a C 3-10 divalent alicyclic hydrocarbon group and a C 6-10 divalent aromatic hydrocarbon group.
  • R 3 represents a hydrocarbon group selected from the group consisting of a C 1-10 aliphatic hydrocarbon group, a C 3-10 alicyclic hydrocarbon group and a C 6-10 aromatic hydrocarbon group.
  • diol units other than the diol unit having a cyclic acetal skeleton are not particularly limited, and examples thereof include units derived from: aliphatic diols such as ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol and neopentylglycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; alicyclic diols such as 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, ali
  • polyester resin of the present invention units derived from ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol are preferred, and units derived from ethylene glycol are particularly preferred.
  • the diol units listed above may be used solely or in combination.
  • the ratio of the diol unit having a cyclic acetal skeleton in the diol unit in the polyester resin (D) of the present embodiment is 1 to 80 mol%, preferably 2 to 60 mol%, and more preferably 5 to 50 mol%.
  • the dicarboxylic acid unit of the polyester resin (D) of the present embodiment is not particularly limited, but examples thereof include units derived from: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid and pentacyclododecanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-
  • units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are preferred, and terephthalic acid, 2,6-naphthalenedicarboxylic acid and isophthalic acid are particularly preferred.
  • units derived from terephthalic acid are preferred, and by using 2,6-naphthalenedicarboxylic acid, transparency and gas barrier properties can be improved.
  • the dicarboxylic acids listed above may be used solely or in combination.
  • 1 to 100 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton and 0 to 99 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a naphthalene skeleton.
  • the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton and 0 to 55 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a naphthalene skeleton.
  • 70 to 100 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton and 0 to 30 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a naphthalene skeleton.
  • Monoalcohol units such as butyl alcohol, hexyl alcohol and octyl alcohol, units derived from polyalcohols (trivalent or higher) such as trimethylolpropane, glycerin and pentaerythritol, units derived from monocarboxylic acids such as benzoic acid, propionic acid and butyric acid, and units derived from polyvalent carboxylic acids (trivalent or higher) such as trimellitic acid, trimesic acid and pyromellitic acid may also be introduced into the polyester resin (D) without departing from the purpose of the present invention.
  • polyalcohols trivalent or higher
  • monocarboxylic acids such as benzoic acid, propionic acid and butyric acid
  • polyvalent carboxylic acids trivalent or higher
  • trimellitic acid trimesic acid and pyromellitic acid
  • the method for producing the polyester resin (D) is not particularly limited, and conventionally known methods can be applied thereto. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, a solution polymerization method and a solid phase polymerization method.
  • the temperature difference between the glass-transition temperature (Tg 2 ) of the polyester resin (D) and the glass-transition temperature (Tg 1 ) of the polyester resin (A) is set to be preferably 50°C or less, more preferably 40°C or less, and even more preferably 30°C or less.
  • Tg 1 and Tg 2 When the temperature difference between Tg 1 and Tg 2 is 50°C or more, problems of poor outer appearance and the like such as thickness unevenness and whitening caused by blow molding may be caused.
  • the limiting viscosity of the polyester resin (D) is preferably 0.3 to 1.2 (dL/g), more preferably 0.5 to 1.0 (dL/g), and even more preferably 0.6 to 0.8 (dL/g).
  • the limiting viscosity is less than 0.3, reduction in moldability and strength is caused, and when the limiting viscosity exceeds 1.2, it is difficult to carry out molding.
  • the mixed resin (B) to be used in the present embodiment can be produced by a dry-blending method in which pellets of the polyamide resin (C) and the polyester resin (D) are subjected to dry blending, or a melt-blending method in which the polyamide resin (C) and the polyester resin (D) are melt-extruded to be re-pelletized. Note that an appropriate formulation is selected depending on intended use, conditions for use, mechanical performance, etc.
  • the weight ratio between the polyamide resin (C) and the polyester resin (D) in the mixed resin (B) ((C)/(D)) is 99/1 to 10/90, preferably 97/3 to 20/80, more preferably 95/5 to 30/70, even more preferably 92/8 to 50/50, and particularly preferably 88/12 to 70/30.
  • the weight ratio of the polyester resin (D) is less than 1%, effects of improving peeling resistance cannot be obtained. Further, when the weight ratio of the polyester resin (D) exceeds 90%, effects of improving peeling resistance can be obtained, but good barrier properties of the polyamide resin (C) are not imparted to the multilayer molding, and therefore it is not practical.
  • thermoplastic resins include thermoplastic polyester resins such as polyethylene-2,6-naphthalene dicarboxylate, polyolefin-based resins, polycarbonate, polyacrylonitrile, polyvinyl chloride and polystyrene.
  • the blending amount of the other thermoplastic resins is preferably 30 wt% or less, more preferably 20 wt% or less, and even more preferably 10 wt% or less of the total amount of the mixed resin (B).
  • the mixed resin (B) may contain at least one metal element selected from the group consisting of a transition metal belonging to Group VIII of the periodic table, manganese, copper and zinc. When the metal element is contained, oxidation of the mixed resin (B) is promoted, and oxygen absorption function is exerted.
  • the metal element is preferably added to the polyamide resin (C) in the form of a low-acid-number inorganic acid salt, organic acid salt or complex salt of the metal element (hereinafter collectively referred to as the "metal catalyst compound").
  • the inorganic acid salt include halides such as chlorides and bromides, sulfates, nitrates, phosphates and silicates.
  • the organic acid salt include carboxylates, sulfonates and phosphonates.
  • the complex salt include transition metal complexes with ⁇ -diketone, ⁇ -keto acid ester or the like.
  • carboxylates, halides and acetylacetonate complexes of the aforementioned metal element are preferably used, and stearates, acetates and acetylacetonate complexes are more preferably used.
  • metal element cobalt is particularly preferred because of its excellent oxygen absorption function.
  • One or two or more of the above-described metal catalyst compounds can be added.
  • the amount of the metal element to be added is preferably 0.01 to 0.10 wt%, and more preferably 0.02 to 0.08 wt% relative to the total amount of the polyamide resin (C) and the polyester resin (D).
  • the adding amount is less than 0.01 wt%, oxygen absorption function is not sufficiently exerted, and the effect of improving oxygen barrier properties of the multilayer molding becomes low.
  • the adding amount is more than 0.10 wt%, the effect of oxygen barrier properties of the multilayer molding is not further improved, and therefore it is uneconomical.
  • a portion having a low stretching magnification (1 to 2.5-fold) may be generated depending on the shape thereof
  • a layer made of the mixed resin (B) in the portion having a low stretching magnification absorbs water, whitening may occur.
  • a whitening preventing agent to the mixed resin (B) according to need, whitening is suppressed and a multilayer molding having good transparency can be obtained thereby.
  • the whitening preventing agent to be used in the present embodiment is a C 18-50 fatty acid metal salt, and preferably a C 18-34 fatty acid metal salt. Whitening prevention can be expected when the carbon number is 18 or more. When the carbon number is 50 or less, good homogeneous dispersion in the mixed resin (B) can be obtained.
  • the fatty acid may have a side chain or double bond, but a linear saturated fatty acid such as stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanoic acid (C28) and triacontanoic acid (C30) is preferred.
  • the metal which forms a salt with the fatty acid is not particularly limited. Examples thereof include sodium, potassium, lithium, calcium, barium, magnesium, strontium, aluminium and zinc. Particularly preferred are sodium, potassium, lithium, calcium, aluminium and zinc.
  • the particle size of the fatty acid metal salt is not particularly limited. However, since it becomes easier to obtain homogeneous dispersion in the mixed resin (B) when the particle size is smaller, the particle size is preferably 0.2 mm or less.
  • the amount of the fatty acid metal salt to be added is preferably 0.005 to 1.0 parts by weight, more preferably 0.05 to 0.5 parts by weight, and particularly preferably 0.12 to 0.5 parts by weight relative to the total amount (100 parts by weight) of the polyamide resin (C) and the polyester resin (D).
  • the fatty acid metal salt in an amount of 0.005 parts by weight or more relative to the total amount (100 parts by weight), the whitening prevention effect can be expected.
  • the adding amount is 1.0 parts by weight or less relative to the total amount (100 parts by weight), the haze value of a multilayer molding obtained can be kept at a low level.
  • a compound selected from the below-described diamide compound and the diester compound may be added as the whitening preventing agent.
  • One or two or more types of diamide compounds may be added.
  • one or two or more types of diester compounds may be added.
  • one or two or more types of diamide compounds may be used in combination with one or two or more types of diester compounds.
  • the diamide compound is obtained from a C 8-30 fatty acid and a C 2-10 diamine.
  • the carbon number of the fatty acid is 8 or more and the carbon number of the diamine is 2 or more, the whitening prevention effect can be expected.
  • the carbon number of the fatty acid is 30 or less and the carbon number of the diamine is 10 or less, good homogeneous dispersion in the mixed resin (B) can be obtained.
  • the fatty acid may have a side chain or double bond, but is preferably a linear saturated fatty acid.
  • Examples of the fatty acid component of the diamide compound include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanoic acid (C28) and triacontanoic acid (C30).
  • Examples of the diamine component of the diamide compound include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine and bis(aminomethyl)cyclohexane. The diamide compound obtained by using the above-described components in combination is used in the present invention.
  • a diamide compound which is obtained from a C 8-30 fatty acid and a diamine mainly composed of ethylenediamine, or a diamide compound which is obtained from a fatty acid mainly composed of montanoic acid and a C 2-10 diamine is preferred.
  • the diester compound is obtained from a C 8-30 fatty acid and a C 2-10 diol.
  • the carbon number of the fatty acid is 8 or more and the carbon number of the diol is 2 or more, the whitening prevention effect can be expected.
  • the carbon number of the fatty acid is 30 or less and the carbon number of the diol is 10 or less, good homogeneous dispersion in the mixed resin (B) can be obtained.
  • the fatty acid may have a side chain or double bond, but is preferably a linear saturated fatty acid.
  • Examples of the fatty acid component of the diester compound include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanoic acid (C28) and triacontanoic acid (C30).
  • Examples of the diol component of the diester compound include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol and cyclohexanedimethanol.
  • the diester compound obtained by using the above-described components in combination is used in the present invention.
  • a diester compound obtained from a fatty acid mainly composed of montanoic acid and a diol mainly composed of ethylene glycol and/or 1,3-butanediol is particularly preferred.
  • the amount of the diamide compound and/or the diester compound to be added is preferably 0.005 to 1.0 parts by weight, more preferably 0.05 to 0.5 parts by weight, and particularly preferably 0.12 to 0.5 parts by weight relative to the total amount (100 parts by weight) of the polyamide resin (C) and the polyester resin (D).
  • the diamide compound and/or the diester compound in an amount of 0.005 parts by weight or more relative to the total amount (100 parts by weight), the whitening prevention effect can be expected.
  • the adding amount is 1.0 parts by weight or less relative to the total amount (100 parts by weight), the haze value of a multilayer molding obtained can be kept at a low level.
  • a conventionally known mixing method can be employed for adding the whitening preventing agent to the mixed resin (B).
  • pellets of the polyamide resin (C) and the polyester resin (D), the metal catalyst compound and the whitening preventing agent may be put into a rotary hollow vessel to be mixed together.
  • a method in which a polyamide resin composition containing a high-concentration whitening preventing agent is produced, then it is diluted with a polyamide resin pellet not containing the whitening preventing agent at a predetermined concentration and the obtained mixture is melted and kneaded a method in which melting and kneading is carried out and subsequently molding is carried out, for example, by means of injection molding, or the like can be employed.
  • the whitening preventing agent When used, it can prevent whitening of a layer made of the mixed resin (B) immediately after the production of the multilayer molding according to the molding method of the present invention. In addition, it can prevent whitening of the layer made of the mixed resin (B) after long-term preservation of the multilayer molding under conditions where whitening is not caused or the degree of whitening is not increased.
  • whitening is suppressed at a level similar to that immediately after molding even if the multilayer molding is subjected to high humidity or brought into contact with water or boiling water or heated to the glass transition temperature or higher after preserved for a long period of time under conditions where whitening is not caused or the degree of whitening is not increased without addition of the whitening preventing agent, for example, in an atmosphere with temperature of 23°C and humidity of 50%RH.
  • the shape of the multilayer molding of the present embodiment is not particularly limited. Examples thereof include a vessel shape, a sheet shape and a stretched film shape.
  • vessel-shaped moldings include a hollow vessel, a tray and a container.
  • the hollow vessel include a hollow vessel made by injection blow molding and a hollow vessel made by direct blow molding.
  • the multilayer molding of the present embodiment is a hollow vessel made by injection blow molding
  • the multilayer molding made by injection blow molding usually has a structure having 3 or more layers.
  • the multilayer molding is obtained by using an injection molding machine having 2 injection cylinders, wherein: the polyester resin (A) and the mixed resin (B) having gas barrier properties are injected into a mold cavity through a mold hot runner from the respective injection cylinders at the surface layer side and the core side to obtain a multilayer parison; and the multilayer parison is further subjected to biaxial stretch blow molding.
  • Blow molding of the multilayer parison may be carried out according to a conventionally known method.
  • a method in which the surface of the multilayer parison is heated to 80 to 120°C and then blow molding is carried out, or a method in which the mouth portion of the multilayer parison is heated to be crystallized, the surface of the multilayer parison is heated to 80 to 120°C and then blow molding is carried out with a mold at 90 to 150°C can be employed.
  • the blow pressure is usually 0.5 to 4 MPa.
  • the polyester resin (A) constituting the outer surface layer and the inner surface layer from the surface layer-side injection cylinder and injecting the mixed resin (B) constituting the core layer from the core side injection cylinder firstly the polyester resin (A) is injected, then the mixed resin (B) and the polyester resin (A) are injected simultaneously, and then the polyester resin (A) is injected in a required amount to fill a mold cavity, thereby producing a multilayer parison having a three-layer structure (polyester resin (A)/mixed resin (B)/polyester resin (A)).
  • the polyester resin (A) constituting the outer surface layer and the inner surface layer from the surface layer-side injection cylinder and injecting the mixed resin (B) constituting the core layer from the core side injection cylinder firstly the polyester resin (A) is injected, then the mixed resin (B) alone is injected, and finally the polyester resin (A) is injected to fill a mold cavity, thereby producing a multilayer parison having a five-layer structure (polyester resin (A)/mixed resin (B)/polyester resin (A)/mixed resin (B)/polyester resin (A)).
  • the method for producing a multilayer parison is not limited to the above-described methods.
  • the thickness of the surface layer containing the polyester resin (A) is preferably 0.01 to 1.0 mm, and the thickness of the core layer composed of the mixed resin (B) is preferably 0.005 to 0.2 mm. Further, the thickness of the hollow vessel is not required to be constant over the whole vessel, and is usually 0.2 to 1.0 mm.
  • gas barrier performance can be exerted when the core layer composed of the mixed resin (B) exists at least at the barrel portion of the hollow vessel, but better gas barrier performance can be obtained when the core layer is extended to the vicinity of the end of the cap section of the hollow vessel.
  • the weight of the layer composed of the mixed resin (B) is preferably 1 to 30 wt%, and more preferably 2 to 20 wt% relative to the total weight of the hollow vessel.
  • the weight of the layer composed of the mixed resin (B) is less than 1 wt%, gas barrier properties of the hollow vessel may be insufficient and therefore it is not preferred.
  • the weight of the layer composed of the mixed resin (B) is more than 30 wt%, it may be difficult to mold the multilayer parison as a precursor into the hollow vessel, and therefore it is not preferred.
  • the shape of the hollow vessel is not limited to a shape in which the concavo-convex portion or bent portion is few, and high design flexibility can be obtained.
  • the hollow vessel of the present invention has excellent aroma retaining properties, it is preferably used for storage and preservation of various articles including: liquid beverages such as carbonated drink, juice, water, milk, sake, whiskey, shochu, coffee, tea, jelly beverage and health beverage; seasonings such as liquid seasoning, sauce, soy sauce, dressing and liquid stock; liquid-type foods such as liquid soup; liquid-type pharmaceutical products; lotion; milky lotion; hairdressing; hair dye; and shampoo.
  • liquid beverages such as carbonated drink, juice, water, milk, sake, whiskey, shochu, coffee, tea, jelly beverage and health beverage
  • seasonings such as liquid seasoning, sauce, soy sauce, dressing and liquid stock
  • liquid-type foods such as liquid soup
  • liquid-type pharmaceutical products such as liquid soup
  • lotion milky lotion
  • hairdressing hair dye
  • hair dye hair dye
  • the multilayer molding of the present embodiment is a multilayer sheet
  • the method for preparing a multilayer sheet is not particularly limited, and a conventionally known multilayering technique such as extrusion molding, coextrusion, laminating and deposition can be used.
  • extrusion molding a single screw extruder or a twin screw extruder may be used, and the temperature of the extruder is preferably 200 to 290°C, and more preferably 210 to 280°C.
  • the multilayer sheet of the present embodiment at least has the core layer composed of the mixed resin (B) and a layer composed of a resin containing 70 wt% or more of the thermoplastic polyester resin (A) in contact therewith.
  • the multilayer sheet may also have a layer composed of a transparent resin (E) consisting of at least one transparent resin selected from the group consisting of a polyester resin other than the polyester resin (A) and the polyester resin (D), an acrylic resin, a polystyrene resin, a polycarbonate resin, a methyl methacrylate-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, a vinyl chloride resin and an alicyclic polyolefin resin.
  • polyester resin other than the polyester resin (A) and the polyester resin (D) polyethylenenaphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate and polyarylate are preferred.
  • a multilayer sheet-forming machine having at least one surface layer-side extrusion cylinder and at least one core side extrusion cylinder can be used.
  • a resin containing 70 wt% or more of the thermoplastic polyester resin (A) is extruded from the surface layer-side extrusion cylinder or from at least one of the surface layer-side extrusion cylinder and the core side extrusion cylinder to form the resin layer, and the mixed resin (B) is extruded from the at least one core side extrusion cylinder to form at least one core layer in contact with the resin layer composed of resin containing the polyester resin (A), thereby obtaining the multilayer sheet.
  • thermoplastic polyester resin (A) to be used in the multilayer sheet edge portions of the multilayer sheet and an end material generated at the time of producing a multilayer sheet vessel obtained by molding the multilayer sheet as described below can be blended (hereinafter, a resin obtained by blending the end material of the multilayer sheet in the polyester resin (A) is referred to as "the polyester resin (A')").
  • the edge portions of the multilayer sheet and the end material generated at the time of producing the multilayer sheet vessel can also be blended in the transparent resin (E) (hereinafter, a resin obtained by blending the end material of the multilayer sheet in the transparent resin (E) is referred to as "the transparent resin (E')").
  • the structure of the multilayer sheet of the present embodiment may be selected according to an intended use of the sheet, and examples thereof include: polyester resin (A)/mixed resin (B)/polyester resin (A) or polyester resin (A')/mixed resin (B)/polyester resin (A') (a three-layer structure consisting of two types of layers); polyester resin (A)/mixed resin (B)/polyester resin (A') or polyester resin (A)/mixed resin (B)/transparent resin (E) or polyester resin (A)/mixed resin (B)/transparent resin (E') or polyester resin (A')/mixed resin (B)/transparent resin (E) or polyester resin (A')/mixed resin (B)/transparent resin (E) or polyester resin (A')/mixed resin (B)/transparent resin (E') (a three-layer structure consisting of three types of layers); polyester resin (A)/mixed resin (B)/polyester resin (A)
  • polyester resin (A)/mixed resin (B)/polyester resin (A) (a three-layer structure consisting of two types of layers); polyester resin (A)/mixed resin (B)/polyester resin (A') (a three-layer structure consisting of three types of layers); polyester resin (A)/mixed resin (B)/polyester resin (A)/mixed resin (B)/polyester resin (A) (a five-layer structure consisting of two types of layers); and polyester resin (A)/polyester resin (A')/mixed resin (B)/polyester resin (A')/polyester resin (A) or polyester resin (A)/mixed resin (B)/polyester resin (A')/mixed resin (B)/polyester resin (A) (a five-layer structure consisting of three types of layers).
  • the multilayer sheet is a sheet of polyester resin (A)/mixed resin (B)/polyester resin (A) (a three-layer structure consisting of two types of layers), it can be produced, for example, by extruding a resin containing 70 wt% or more of the thermoplastic polyester resin (A) from a surface layer-side extrusion cylinder and extruding the mixed resin (B) from a core layer-side extrusion cylinder.
  • the multilayer sheet is a sheet of polyester resin (A)/mixed resin (B)/polyester resin (A') (a three-layer structure consisting of three types of layers)
  • it can be produced, for example, by using a multilayer sheet-forming machine having 2 surface layer-side extrusion cylinders and a core layer-side extrusion cylinder, wherein: a resin containing 70 wt% or more of the thermoplastic polyester resin (A) is extruded from one surface layer-side extrusion cylinder; the thermoplastic polyester (A') is extruded from the other surface layer-side extrusion cylinder; and the mixed resin (B) is extruded from the core layer-side extrusion cylinder.
  • the multilayer sheet is a sheet of polyester resin (A)/mixed resin (B)/polyester resin (A)/mixed resin (B)/polyester resin (A) (a five-layer structure consisting of two types of layers)
  • it can be produced, for example, by using a multilayer sheet-forming machine having a surface layer-side extrusion cylinder, an interlayer-side extrusion cylinder and a central layer extrusion cylinder, wherein: a resin containing 70 wt% or more of the thermoplastic polyester resin (A) is extruded from the surface layer-side extrusion cylinder and the central layer extrusion cylinder; and the mixed resin (B) is extruded from the interlayer-side extrusion cylinder.
  • the multilayer sheet is a sheet of polyester resin (A)/polyester resin (A')/mixed resin (B)/polyester resin (A')/polyester resin (A) (a five-layer structure consisting of three types of layers)
  • it can be produced, for example, by using a multilayer sheet-forming machine having a surface layer-side extrusion cylinder, an interlayer-side extrusion cylinder and a central layer extrusion cylinder, wherein: a resin containing 70 wt% or more of the thermoplastic polyester resin (A) is extruded from the surface layer-side extrusion cylinder; the thermoplastic polyester resin (A') is extruded from the interlayer-side extrusion cylinder; and the mixed resin (B) is extruded from the central layer extrusion cylinder.
  • the multilayer sheet is a sheet of polyester resin (A)/mixed resin (B)/polyester resin (A')/mixed resin (B)/polyester resin (A) (a five-layer structure consisting of three types of layers)
  • it can be produced, for example, by using a multilayer sheet-forming machine having a surface layer-side extrusion cylinder, an interlayer-side extrusion cylinder and a central layer extrusion cylinder, wherein: a resin containing 70 wt% or more of the thermoplastic polyester resin (A) is extruded from the surface layer-side extrusion cylinder; the mixed resin (B) is extruded from the interlayer-side extrusion cylinder; and the thermoplastic polyester resin (A') is extruded from the central layer extrusion cylinder.
  • each layer of the multilayer sheet of the present embodiment may be suitably selected according to an intended use of the sheet, but the thickness of the layer made of the mixed resin (B) is preferably 1 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 80 ⁇ m.
  • the thickness of the surface layer containing the polyester resin (A) is preferably 50 to 1000 ⁇ m, more preferably 100 to 800 ⁇ m, and even more preferably 200 to 600 ⁇ m.
  • the thickness of the entire multilayer sheet is preferably 100 to 2000 ⁇ m, more preferably 200 to 1600 ⁇ m, and even more preferably 400 to 1200 ⁇ m.
  • the weight of the layer made of the mixed resin (B) in the multilayer sheet of the present embodiment is preferably 1 o 30 wt%, and more preferably 2 to 20 wt% relative to the total weight of the multilayer sheet.
  • the weight of the layer made of the mixed resin (B) is less than 1 wt%, gas barrier properties of the multilayer sheet may be insufficient, and therefore it is not preferred.
  • the weight of the layer made of the mixed resin (B) is more than 30 wt%, it may be difficult to form a vessel or the like using the multilayer sheet, and therefore it is not preferred.
  • the method for producing a tray- or container-shaped multilayer molding is not particularly limited.
  • a pressure forming machine, vacuum forming machine, vacuum pressure forming machine or the like the surface of the multilayer sheet is rapidly heated to 90 to 250°C to be softened, and then it is molded using a mold having a desired shape, thereby obtaining a vessel (multilayer sheet vessel).
  • the thickness of the multilayer sheet vessel of the present embodiment is preferably 5 to 2000 ⁇ m, more preferably 20 to 1800 ⁇ m, and even more preferably 30 to 1500 ⁇ m.
  • the haze value of the multilayer sheet vessel of the present embodiment is preferably 15% or less.
  • the weight of the layer made of the mixed resin (B) in the multilayer sheet vessel of the present embodiment is preferably 1 to 30 wt%, and more preferably 2 to 20 wt% relative to the total weight of the multilayer sheet vessel.
  • the weight of the layer made of the mixed resin (B) is less than 1 wt%, gas barrier properties of the multilayer sheet vessel may be insufficient, and therefore it is not preferred.
  • the weight of the layer made of the mixed resin (B) is more than 30 wt%, it may be difficult to mold the multilayer sheet as a precursor into the multilayer sheet vessel, and therefore it is not preferred.
  • materials recovered from polyethylene terephthalate products materials recovered from modified polyethylene terephthalate products containing a small amount of an isophthalic acid component unit, materials recovered from polyamide products, and/or end materials at the time of the production of molded products, and materials recovered from polyester and/or polyamide resins of non-standard products, etc. may be added to a layer containing the polyester resin (A) within a range in which the effects of the present invention are not reduced.
  • the content to be put into the multilayer sheet vessel of the present embodiment is not particularly limited, and examples thereof include foods, cosmetics, pharmaceutical products, toiletries, mechanical/electrical/electronic parts, oils and resins.
  • the multilayer molding of the present embodiment can be suitably used, in particular, as a vessel for preserving foods.
  • the shape of the multilayer molding is not limited to a shape in which the concavo-convex portion or bent portion is few, and therefore higher design flexibility can be obtained.
  • the multilayer molding of the present invention is preferable for storage and preservation of various articles including: gel-type foods such as tofu (soybean curd), egg-tofu, jelly, pudding, mizu-youkan (soft sweet jellied bean paste), mousse, yogurt and Chinese-style almond jelly; jam, miso (soybean paste), seasoning for Japanese-style pickles, spices such as grated spices; processed meat products such as salami, ham, sausage, yakitori (grilled chicken pieces), meatball, hamburger, roasted pork and beef jerky; processed seafood products such as kamaboko (boiled fish paste), boiled shellfish, boiled fish and chikuwa (tube-shaped fish paste cake); processed rice products such as watery cooked rice, cooked rice, boiled rice mixed with fish (meat) and vegetables and glutinous rice steamed with red adzuki beans; processed milk products such as cheese, butter, cream and condensed milk; processed egg products such as boiled egg and soft boiled egg; side dishes such as boiled vegetables, boiled beans
  • composition of each of the structural units was calculated by means of the 1 H-NMR measurement. The measurement was carried out at 500 MHz using BRUKER AVANCE-500III manufactured by BRUKER. Regarding solvents, trifluoroacetic acid-d was used for evaluating the polyester resin (A) and the polyamide resin (C), and deuterochloroform was used for evaluating the polyester resin (D).
  • the measurement was carried out using a heat flux differential scanning calorimeter (model: DSC-50) manufactured by Shimadzu Corporation.
  • the temperature raising rate was set at 20°C/min.
  • the measurement was carried out using Capirograph 1C manufactured by Toyo Seiki Co., Ltd. (temperature: 260°C, preheating time: 1 min, nozzle diameter: 1 mm, nozzle length: 10 mm, shear rate: 100 (1/sec)).
  • a hollow vessel was cut to cause delamination, and then the thickness at a position 75 mm away from the bottom of the hollow vessel was measured using a micrometer. Note that the measurement was carried out at 3 points in the circumferential direction (0°, 120°, 240°), and the thickness was calculated based on the arithmetical mean of the measurement values. (7) Thickness of multilayer sheet
  • the multilayer sheet vessel was cut, and using a micrometer, the bottom of the vessel and the overall thickness of the bottom of the vessel were measured. After delamination was caused, the thickness of the core layer was measured.
  • the measurement was carried out according to JIS-K-7105, ASTM D1003 using a haze meter (model: COH-300A) manufactured by Nippon Denshoku Industries Co., Ltd. (10) Delamination properties of hollow vessel (evaluation of delamination by impact test of the side of the vessel) Test method: the multilayer molding was filled with water, the cap of the molding was tightened, and it was allowed to stand for 24 hours.
  • the side of the multilayer molding was impacted by a pendulum-type hammer having a projection having a width of 20 mm and Rlmm (weight: 1 kg, distance between the rotation axis and the center of gravity: 27 cm) being swung down with a lifting angle of 90°, and the presence or absence of delamination was judged by visual observation, and the number of times of impact given until delamination was caused was measured.
  • the multilayer molding was cut to a piece having a width of 15 mm, and using Strograph manufactured by Toyo Seiki Co., Ltd., T-peel test was carried out at a rate of 50 mm/min. The maximum point load at the time of delamination was measured, this was regarded as the T-peel load, and the interlayer strength was evaluated. Note that the number of times of the measurement was 10 in each case, and based on the arithmetical mean of the measurement values, the interlayer strength was calculated.
  • the vessel was filled with 50 ml of water, and then it was heat-sealed with a film made of polyethylene terephthalate. After that, it was allowed to stand in an environment of 23°C and 50%RH for 24 hours. After that, it was horizontally dropped from a height of 200 cm onto a concrete surface, and the presence or absence of delamination was judged by visual observation, and the number of times of drop given until delamination was caused was measured.
  • the measurement was carried out according to ASTM D3985 under the following atmosphere: temperature: 23°C, relative humidity of the inside of the multilayer molding: 100%, relative humidity of the outside: 50%.
  • OX-TRAN 10/50A manufactured by Modern Controls Incorporated was used for the measurement.
  • terephthalic acid and ethylene glycol were fed in the amounts described in Table 1, and an esterification reaction was performed according to the ordinary method.
  • ethylene glycol for depolymerization and germanium dioxide were added in the amounts described in Table 1, and it was subjected to depolymerization at 225°C under a nitrogen gas stream. The reaction was performed for 3 hours while water produced being distilled away. After that, ethylene glycol was distilled away at 215°C and 13.3 kPa.
  • raw material monomers specifically, methyl 2,6-naphthalenedicarboxylate, dimethyl terephthalate, ethylene glycol and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (SPG)
  • SPG 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane
  • a hollow vessel having a three-layer structure was molded using materials descried below: Outer surface layer and inner surface layer
  • the evaluation results of the obtained three-layer vessel are shown in Table 4.
  • the evaluation results of the obtained three-layer vessel are shown in Table 4.
  • the evaluation results of the obtained three-layer vessel are shown in Table 5.
  • the evaluation results of the obtained three-layer vessel are shown in Table 5.
  • the evaluation results of the obtained three-layer vessel are shown in Table 5.
  • a hollow vessel having a three-layer structure was molded in a manner similar to that in Example 1, except that as a resin constituting the core layer, the polyamide resin (C) was used.
  • the evaluation results of the obtained three-layer vessel are shown in Table 5.
  • the polyester resin (A) was extruded from the second and third extruders respectively at 270°C to produce a multilayer sheet having a three-layer structure consisting of two types of layers in which the layer structure thereof is surface layer (polyester resin (A), 270 ⁇ m)/gas barrier layer (mixed
  • thermoforming was carried out when the temperature of the sheet surface reached 120°C, thereby obtaining a cup-shaped vessel having an opening of 70 x 70 mm, a depth of 26 mm and a capacity of 100 ml.
  • the evaluation results of the obtained multilayer sheet are shown in Table 6, and the evaluation results of the cup-shaped multilayer sheet vessel are shown in Table 7.
  • the evaluation results of the obtained multilayer sheet are shown in Table 6, and the evaluation results of the multilayer sheet vessel are shown in Table 7.
  • the evaluation results of the obtained multilayer sheet are shown in Table 6, and the evaluation results of the multilayer sheet vessel are shown in Table 7.
  • the evaluation results of the obtained multilayer sheet are shown in Table 6, and the evaluation results of the multilayer sheet vessel are shown in Table 7.
  • the evaluation results of the obtained multilayer sheet are shown in Table 6, and the evaluation results of the multilayer sheet vessel are shown in Table 7.
  • a multilayer sheet having a three-layer structure was molded in a manner similar to that in Example 6, except that as a resin constituting the core layer, the polyamide resin (C) was used, and a cup-shaped multilayer sheet vessel was molded.
  • the evaluation results of the obtained multilayer sheet are shown in Table 6, and the evaluation results of the multilayer sheet vessel are shown in Table 7.
  • polyester resin D1 D2 Components blended at the time of polymerization PTA g 45871 48022 SPG g 9245 6159 EG g 19365 20273 EG for depolymerization g 18337 19197 GeO 2 g 7.2 7.5 TBT g 4.7 4.9 AcOK g 5.4 5.7 TEP g 25.1 26.3 Evaluation results of polyester SPG mol% 6 10 Glass transition temperature °C 85 87 Limiting viscosity dl/g 0.69 0.68 Melt viscosity Pa ⁇ s 470 450
  • the multilayer molding of the present invention has excellent transparency and gas barrier properties, wherein delamination due to drop or impact does not easily occur, and therefore it is suitably used as a vessel for various articles such as liquid beverages, seasonings, liquid-type foods, liquid-type pharmaceutical products and cosmetics.

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  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Polyamides (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Claims (14)

  1. Pièce moulée multicouche faite en résine comprenant trois ou plus de trois couches de résine, dans laquelle au moins une couche de résine de la pièce moulée multicouche est configurée à partir d'une résine mixte (B) contenant, en un rapport (C)/(D) de 99/1 à 10/90 en poids, une résine de polyamide (C) obtenue par polymérisation d'un composant diamine contenant 70 % en moles ou plus de m-xylylènediamine et d'un composant acide dicarboxylique contenant 70 % en moles ou plus d'acide adipique, et une résine de polyester (D) contenant une unité acide dicarboxylique et une unité diol, 1 à 80 % en moles de l'unité diol ayant un squelette d'acétal cyclique ; et au moins une couche de résine en contact avec une couche configurée à partir de la résine mixte (B) et les couches de résine formant les deux surfaces de la pièce moulée multicouche sont configurées à partir d'une résine contenant 70 % en poids ou plus d'une résine de polyester thermoplastique (A) obtenue par polymérisation d'un composant acide dicarboxylique contenant 80 % en moles ou plus d'acide téréphtalique et d'un composant diol contenant 80 % en moles ou plus d'éthylène glycol.
  2. Pièce moulée multicouche selon la revendication 1, dans laquelle l'unité diol ayant le squelette d'acétal cyclique de la résine de polyester (D) est une unité diol dérivée de 3,9-bis(1,1-diméthyl-2-hydroxyéthyl)-2,4,8,10-tétraoxaspiro[5.5]undécane ou une unité diol dérivée de 5-méthylol-5-éthyl-2-(1,1-diméthyl-2-hydroxyéthyl)-1,3-dioxane.
  3. Pièce moulée multicouche selon la revendication 1 ou 2, dans laquelle l'unité diol autre que l'unité diol ayant un squelette d'acétal cyclique de la résine de polyester (D) est une unité diol dérivée d'au moins un diol choisi dans le groupe constitué par l'éthylène glycol, le diéthylène glycol, le triméthylène glycol, le 1,4-butanediol et le 1,4-cyclohexanediméthanol.
  4. Pièce moulée multicouche selon l'une quelconque des revendications 1 à 3, dans laquelle l'unité acide dicarboxylique de la résine de polyester (D) est une unité acide dicarboxylique dérivée d'au moins un acide dicarboxylique choisi dans le groupe constitué par l'acide téréphtalique, l'acide isophtalique, l'acide 1,4-naphtalènedicarboxylique, l'acide 1,5-naphtalènedicarboxylique, l'acide 2,6-naphtalènedicarboxylique et l'acide 2,7-naphtalènedicarboxylique.
  5. Pièce moulée multicouche selon l'une quelconque des revendications 1 à 4, dans laquelle la résine de polyamide (C) est une résine de polyamide polymérisée en phase solide obtenue par polycondensation à l'état fondu du composant diamine contenant 70 % en moles ou plus de m-xylylènediamine et du composant acide dicarboxylique contenant 70 % en moles ou plus d'acide adipique, et en outre soumission de la résine de polyamide obtenue à une polymérisation en phase solide.
  6. Pièce moulée multicouche selon l'une quelconque des revendications 1 à 5, dans laquelle la résine mixte (B) contient en outre 0,01 à 0,10 % en poids d'au moins un élément métallique choisi dans le groupe constitué par un métal de transition appartenant au Groupe VIII du Tableau Périodique, le manganèse, le cuivre et le zinc.
  7. Pièce moulée multicouche selon l'une quelconque des revendications 1 à 6, comprenant : une couche de surface extérieure ; une couche de surface intérieure ; et au moins une couche de cœur positionnée entre la couche de surface extérieure et la couche de surface intérieure, qui est produite en utilisant une machine de moulage par injection ayant un cylindre d'injection du côté couche de surface et un cylindre d'injection du côté cœur, et qui est un récipient creux obtenu par moulage-soufflage d'une paraison multicouche, qui est obtenue par injection de la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) à partir du cylindre d'injection du côté couche de surface pour former la couche de surface extérieure et la couche de surface intérieure et injection de la résine mixte (B) à partir du cylindre d'injection du côté cœur pour former l'au moins une couche de cœur.
  8. Pièce moulée multicouche selon la revendication 7, qui est un récipient creux obtenu par moulage-soufflage d'une paraison ayant une structure à trois couches, qui est formée par remplissage d'une cavité de moule par : injection de la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) à partir du cylindre d'injection du côté couche de surface ; puis injection de la résine mixte (B) à partir du cylindre d'injection du côté cœur et injection de la résine de polyester thermoplastique (A) à partir du cylindre d'injection du côté couche de surface en même temps ; et ensuite injection de la résine de polyester thermoplastique (A) à partir du cylindre d'injection du côté couche de surface.
  9. Pièce moulée multicouche selon la revendication 7, qui est un récipient creux obtenu par moulage-soufflage d'une paraison ayant une structure à cinq couches, qui est formée par remplissage d'une cavité de moule par : injection de la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) à partir du cylindre d'injection du côté couche de surface ; puis injection de la résine mixte (B) à partir du cylindre d'injection du côté coeur ; et ensuite injection de la résine de polyester thermoplastique (A) à partir du cylindre d'injection du côté couche de surface.
  10. Pièce moulée multicouche selon l'une quelconque des revendications 7 à 9, qui est un récipient creux obtenu par chauffage de la surface de la paraison à une température de 80 à 120 °C, suivi d'un moulage-soufflage de celle-ci.
  11. Pièce moulée multicouche selon l'une quelconque des revendications 1 à 6, comprenant : les deux couches de surface ; et au moins une couche de cœur positionnée entre les deux couches de surface, qui est produit en utilisant une machine de formation de feuille multicouche ayant au moins un cylindre d'extrusion du côté couche de surface et au moins un cylindre d'extrusion du côté cœur, et qui est une feuille multicouche ayant une épaisseur de 100 à 2000 µm obtenue par : extrusion de la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) à partir du cylindre d'extrusion du côté couche de surface, ou du cylindre d'extrusion du côté couche de surface et d'au moins le cylindre d'extrusion du côté cœur pour former une couche de résine ; et extrusion de la résine mixte (B) à partir d'au moins le cylindre d'extrusion du côté cœur pour former l'au moins une couche de cœur en contact avec la couche de résine faite de résine contenant la résine de polyester thermoplastique (A).
  12. Pièce moulée multicouche selon la revendication 11, qui est une feuille multicouche ayant une structure à trois couches obtenue par extrusion de la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) à partir du cylindre d'extrusion du côté couche de surface et extrusion de la résine mixte (B) à partir du cylindre d'extrusion du côté cœur.
  13. Pièce moulée multicouche selon la revendication 11, qui est une feuille multicouche ayant une structure à cinq couches obtenue en utilisant une machine de formation de feuille multicouche ayant un cylindre d'extrusion du côté couche de surface, un cylindre d'extrusion du côté couche intermédiaire et un cylindre d'extrusion du côté couche centrale, dans laquelle : la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) est extrudée à partir du cylindre d'extrusion du côté couche de surface ; la résine mixte (B) est extrudée à partir du cylindre d'extrusion du côté couche intermédiaire ou du cylindre d'extrusion du côté couche centrale ; et la résine contenant 70 % en poids ou plus de la résine de polyester thermoplastique (A) est extrudée à partir du cylindre d'extrusion du côté couche intermédiaire ou du cylindre d'extrusion du côté couche centrale à partir duquel la résine mixte (B) n'est pas extrudée.
  14. Pièce moulée multicouche selon l'une quelconque des revendications 11 à 13, qui est un récipient en feuille multicouche obtenu par chauffage rapide de la surface de la feuille multicouche à une température de 90 à 250 °C pour qu'elle ramollisse, et ensuite moulage de la feuille multicouche par utilisation d'un moule ayant une forme souhaitée.
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